Li4Ti5O12,Li(4-alpha)ZalphaTi5O12 or Li4ZbetaTi(5-beta)O12 particles processes for obtaining same and use as electrochemical generators

ABSTRACT

Synthesis process for new particles of Li 4 Ti 5 O 12 , Li (4-α) Z α Ti 5 O 12  or Li 4 Z β Ti (5-β) O 12 , preferably having a spinel structure, wherein β is greater than 0 and less than or equal to 0.5 (preferably having a spinel structure), α representing a number greater than zero and less than or equal to 0.33, Z representing a source of at least one metal, preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni, Co. These particles coated with a layer of carbon notably exhibit electrochemical properties that are particularly interesting as components of anodes and/or cathodes in electrochemical generators.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No. 10/830,240, filed Apr. 23, 2004, which is a continuation of U.S. application Ser. No. 10/432,999, filed May 29, 2003, which is a §371 national stage application of International Application No. PCT/CA01/01714, filed Dec. 3, 2001, and claims priority to Canadian Application No. 2,327,370, filed Dec. 5, 2000, each of which are hereby incorporated by reference in their entirety.

FIELD OF THE INVENTION

The present invention relates to new particles based on Li₄Ti₅O₁₂, based on Li_((4-α))Z_(α)Ti₅O₁₂, or based on Li₄Z_(β)Ti_((5-β))O₁₂.

The present invention also relates to processes that make it possible to prepare these particles and to their use, especially in the area of electrochemical devices such as electrochemical generators.

DESCRIPTION OF PRIOR ART

Marketing of the lithium-ion battery by Sony, in 1990, was reported by Naguara and Tozawa, Prog. Batt. Solar Cells, 9 (1990), 209. It made possible an expansion and a significant breakthrough of batteries into the area of portable devices (telephone, computer). The technology of Li-ion batteries is based on lithium intercalation electrodes, in particular the anode which is made of graphite. At the time of the first charge, a passivation film is formed on the carbon surface. The chemistry and the composition of this passivation film are complex. The electrochemical formation protocol for this film remains an industrial secret. In addition, at the time of insertion of lithium in carbon, there is a volume variation of 10%, which induces a discontinuity between the particles causing loosening of the interfaces between the electrode and the electrolyte, and between the electrode and the current collector.

Once intercalated (LiC₆), the potential of the carbon gets closer to the one of the lithium deposit, which makes the electrode more reactive. The projection of the small battery to a higher scale for hybrid and electric vehicle applications requires a large quantity of electrolytes which makes the safety aspect much more significant.

Titanium oxide spinel Li₄Ti₅O₁₂ is a material for anodes promising for lithium-ion batteries due to its intercalation potential (K. Zaghib et al., 190^(th) Electrochemical Society Meeting, San Antonio, Abs. no. 93, 1996), cyclability, rapid charging-discharging at high current such as described by K. Zaghib et al. in Proceeding on Lithium Polymer Batteries, PV96-17, p. 223) in The Electrochemical Society Proceeding Series (1996), (K. Zaghib et al., J. Electro chem. Soc. 145, 3135, (1998) and in J. Power Sources, 81-82 (1999) 300-305). The coefficient of diffusion of lithium in Li₄T₅O₁₂ is of a higher order of magnitude than the coefficient of diffusion of lithium in carbons (regarding this subject, see K. Zaghib et al., J. Power Sources, 81-82 (1999) 300-305). This characteristic distinguishes Li₅Ti₅O₁₂ from the other potential candidates for power applications, such as PNGV and GSM pulses. During the intercalation of lithium, the structure of Li₄Ti₅O₁₂ does not vary in volume, which makes this electrode very stable and thus safe. This study was carried out by Ozhuku and reported in J. Electrochem. Soc., 140, 2490 (1993) by X-ray diffraction and by scanning microscopy in situ by Zayhib et al. (and reported in Proceeding on Lithium Polymer Batteries, PV96-17, p. 223 in The Electrochemical Society Proceeding Series (1996) and in J. Electro chem. Soc. 145, 3135, (1998).

The material Li₄Ti₅O₁₂ because of its lack of volume expansion (also called as zero volume expansion (ZEV)) has been easily used in polymer, ceramic or glass electrolyte batteries, which ensures good cycling stability. In addition, the good behavior of this anode at 1.5 V promotes the use of any type of liquid electrode, such as ethylene carbonate (EC), propylene carbonate (PC) or mixtures of these two. At this potential level, there is no passivation film formation on the electrode, which on one hand prevents the release of gas due to the electrolyte reduction, and on the other hand, prevents loss of capacity. This operation potential increases the life span of the battery, especially for stand-by type applications because of its character as electrode without passivation film. The use of Li₄Ti₅O₁₂ as an anode does not require any prior forming of the battery.

In addition, in the configuration of the plastic metal type battery, a secondary pocket is reserved for gas due to electrolyte decomposition when carbon is used as the anode. The fact that the battery with Li₄Ti₅O₁₂ does not need either forming or a reserve pocket for degassing will reduce the manufacturing cost of the battery.

The insertion reaction of Li₄Ti₅O₁₂ occurs as follows:

Li₄Ti₅O₁₂+3Li⁺+3e⁻←→Li₇Ti₅O₁₂  (1)

In the literature (T. Ohzuku, et al., J. Electrochem. Soc., 140, 2490 (1993)) and (J. Schoonman et al., the 198^(th) Meeting of the Electrochemical Society Phoenix, Extend Abstract No. 91, 92 and 98, October 2000), the Li₄Ti₅O₁₂ is mentioned as being able to be obtained by a binary mixture of a mixture of LiOH and TiO₂ where the synthesis temperature is greater than 600° C. Residual impurities of the TiO₂, Li₂TiO₃ and/or other type in the mixture limit the electrode capacity and limit the size of the particles.

In the document entitled “Solid state lithium ion batteries using carbon or an oxide as negative electrode”, J. Electrochem. Soc., Vol. 145, 3135, (1998) K. Zaghib, M. Armand and M. Gauthier describe all the different possible applications of Li₄Ti₅O₁₂ as anode or cathode in rechargeable batteries or supercapacitors.

In the document “Electrochemistry of anodes in solid-state Li-ion polymer batteries” J. Electrochem. Soc., Vol. 145, No. 9, September 1998, the electrochemical performance of solid-state lithium ion batteries that are produced using an electrolyte based on solid polymers free of solvent is described. A cell based on Li₄Ti₅O₁₂ as cathode with lithium as anode, at a rate of C/1 supplies 150 mAh/g, which corresponds to 97% of the efficiency of nominal capacity. The irreversible capacity was high when carbon was used as the negative electrode. However, the sacrificial capacity was very slight when carbon was replaced with a spinel material.

In the document “Electrochemical study of Li ₄ Ti ₅ O ₁₂ , a negative electrode for li-ion polymer rechargeable batteries” K Zaghib et al. give evidence of the electrochemical stability of a negative electrode for lithium ions containing Li₄Ti₅O₁₂ of the same type as that described in the preceding example regarding its coefficient of chemical diffusion for a Li₄Ti₅O₁₂ structure of the spinel type which results in a coefficient of diffusion with a value of −2.10⁻⁸ cm².s⁻¹, which gives a value that is greater in intensity than that of the carbon negative electrodes. Thus the Li₄Ti₅O₁₂ electrode offers advantages for electrochemical cells which are safety, long life span and reliability.

The U.S. Pat. No. 6,221,531 describes a structure of the spinel type with the general formula Li[Ti_(1.67)Li_(0.33-y)M_(y)]O₄, wherein Y<0≦0.33 with M representing magnesium and/or aluminum. This structure is presented as useful for making up a negative electrode for a non-aqueous electrochemical cell and in a non-aqueous battery comprising a plurality of cells, connected electrically, each cell comprising a negative electrode, an electrolyte and a positive electrode, the negative electrode being made up of this spinel structure.

Thus there was a need for new types of particles free of the limitations and/or disadvantages commonly associated with particles of the prior art previously mentioned and, in particular, making possible the production of high-performance electrochemical devices with cycling stability, easy to spread on a support such as an electrode and with good flexibility as regards to the thickness of the electrode that will be produced using these particles.

IN THE DRAWINGS

FIG. 1: illustrates the different applications of the Li₄Ti₅O₁₂ particles (coated with carbon or not) as anode or as cathode for batteries and supercapacitors.

FIG. 2: illustrates comparative performances of a process according to the invention compared with those of a classic process such as described in Prog. Batt. Solar Cells, 9 (1990), 209.

FIG. 3: illustrates the double role of carbon in the preparation process for new particles and in the composition of the carbon layer that coats them.

FIG. 4: illustrates a classic formation process for Li₄Ti₅O₁₂ (macroscopic particle), in the absence of carbon; this process makes it possible to obtain a spinel structure in the presence of impurities of a TiO₂ or other type. This structure is limited for electrochemical performance, to currents less than 2 C.

FIG. 5: illustrates the same process illustrated in FIG. 4, with the exception of the reagent LiOH which is substituted by Li₂CO₃; this type of process yields a formation of agglomerates of the Li₄Ti₅O₁₂ type.

FIG. 6: illustrates a process according to the invention for the formation of nano-particles of Li₄Ti₅O₁₂ from a ternary mixture LiOH—C—TiO₂, intimately mixed at high energy, this mixture is heated at 400° C. then to 600° C. This type of process gives rise to the formation of nano-agglomerates of Li₄T₅O₁₂.

FIG. 7: illustrates a process similar to the one shown in FIG. 6, with the exception that LiOH is substituted by Li₂CO₃; this type of process leads to the formation of Li₄Ti₅O₁₂ nano-agglomerates.

FIG. 8: illustrates a process similar to the one illustrated in FIG. 7, by adding Li₂CO₃ to the initial product; this type of process makes it possible to obtain Li₄Ti₅O₁₂ nano-agglomerates.

FIG. 9: illustrates a process similar to those shown in FIGS. 6 and 7, with the exception that calcination is carried out in an inert atmosphere; this type of process makes it possible to obtain Li₄Ti₅O₁₂ nano-agglomerates of Li₄Ti₅O₁₂ coated with carbon. This structure gives exceptional electrochemical performance at high current density (12 C).

FIG. 10: illustrates the advantages of a pretreatment of the mixture milled at high energy. Dry process. Homogeneous precursor. Homogeneous specific surface area. Coating of particles with carbon. Direct contact of particle with carbon. Direct contact via carbon with the reactive particles. Carbon is a very good thermal conductor. Low contamination. Homogeneous dispersion. Acceleration or rapid synthesis. Obtaining a mixture of nanostructures after the thermal treatment.

FIG. 11: illustrates the mechanism and the role of carbon coating, the latter coating making it possible to obtain a large diffusion of lithium in Li₄Ti₅O₁₂ and obtain 90% of the nominal capacity at 12 C.

FIG. 12: illustrates the mechanism of the technology of hybrid supercapacitors using an anode of the nano-Li₄Ti₅O₁₂ type.

FIG. 13: is the TGA curve of a mixture of TiO₂+Li₂CO₃+carbon after milling at high energy for 2 hours, in air and in argon; the reaction starts at 400° C. (in argon and in air).

FIG. 14: is a SEM photo of microscopic particles of Li₄Ti₅O₁₂ obtained from a mixture of Li₂CO₃+TiO₂.

FIG. 15: is a SEM photo of nanoscopic particles of Li₄Ti₅O₁₂ obtained using a mixture of Li₂CO₃+TiO₂+carbon.

FIG. 16: illustrates a manufacturing process for nanoparticles of Li₄Ti₅O₁₂ coated with carbon and obtained by coating the particles of TiO₂ with organic formulations of the polyol type and/or of the PE-PO type; the thermal treatment carried out in inert atmosphere transforms the organic part into carbon. This process is carried out in the step of mixed Jar milling with solvent or dry.

FIG. 17: illustrates a manufacturing process for nanoparticles of Li₄Ti₅O₁₂ coated with carbon and obtained by coating the particles of TiO₂ with inorganic formulations of the Al₂O₃, ZrO₂ type, the thermal treatment carried out in inert atmosphere transforming the organic part to carbon. This process is carried out in the step of mixed Jar milling with solvent or dry.

FIG. 18: illustrates a manufacturing process for nanoparticles of Li₄Ti₍₅₋₎AlO₁₂ coated with carbon and obtained by coating the particles of TiO₂ using a hybrid inorganic-organic formulation.

SUMMARY OF THE INVENTION

The present invention concerns a synthesis process for new particles of the formula Li₄Ti₅O₁₂, of the formula Li_((4-α))Z_(α)Ti₅O₁₂ or of the formula Li₄Z_(β)Ti_((5-β))O₁₂, wherein α represents a number greater than zero and less than or equal to 0.33, β represents a number greater than 0 and less than or equal to 0.5, Z represents a source of at least one metal, preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni, Co. These particles are coated with a layer of carbon. Use of these particles in electrochemical systems also constitutes an object of the present invention.

DESCRIPTION OF THE INVENTION

A first object of the present invention consists of a process that makes possible the preparation of particles comprising:

-   -   a core of Li₄Ti₅O₁₂, a core of Li_((4-α))Z_(α)Ti₅O₁₂ or a core         of Li₄Z_(β)Ti_((5-β))O₁₂, α representing a number greater than         zero and less than or equal to 0.33, β representing a number         greater than 0 and less than or equal to 0.5, Z representing a         source of at least one metal, preferably chosen from the group         made up of Mg, Nb, Al, Zr, Ni, Co; and     -   a coating of carbon.

According to an advantageous embodiment, this synthesis process makes possible the preparation of particles of Li₄Ti₅O₁₂ (preferably with spinel structure) coated with carbon, said particles comprising from 0.01 to 10%, preferably 1 to 6%, and still more preferably around 2% by weight of carbon, the quantity of carbon being expressed with respect to the total mass of Li₄Ti₅O₁₂ particles;

-   -   said process comprising the steps of         -   a) preparation of a dispersion of a ternary mixture             (preferably an intimate ternary mixture) of             TiO_(x)—Li_(z)Y-carbon, wherein             -   x represents a number between 1 and 2,             -   z represents 1 or 2, and             -   Y represents a radical chosen among CO₃, OH, O and TiO₃                 or a mixture of them; and         -   b) heating of the dispersion obtained in the preceding step,     -   the operating conditions, more specifically the concentration         conditions of components of the ternary mixture submitted to         dispersion, being chosen in such a way as to yield a conversion,         preferably a complete conversion, of the initial products into         Li₄Ti₅O₁₂.

According to another advantageous embodiment, the process according to the invention makes possible the synthesis of particles of Li_((4-α))Z_(α)Ti₅O₁₂ (preferably with spinel structure) coated with carbon, α representing a number greater than zero and less than or equal to 0.33, Z representing a source of at least one metal, preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni, Co, said particles comprising from 0.01 to 10%, preferably 1 to 6%, and still more preferably around 2% by weight of carbon, the quantity of carbon being expressed with respect to the total mass of Li_((4-α))Z_(α)Ti₅O₁₂ particles;

-   -   said process comprising the steps of         -   a) preparation of a dispersion of an intimate ternary             mixture of TiO_(x)LiY-carbon, wherein             -   x represents a number between 1 and 2,             -   z represents 1 or 2, and             -   Y represents a radical chosen among CO₃, OH, O and TiO₃                 or a mixture of them; and         -   b) heating of the dispersion obtained in the preceding step,             preferably at a temperature comprised between 400 and 1,000°             C.,             the operating conditions, more specifically the             concentration conditions of components of the ternary             mixture submitted to dispersion, being chosen in such a way             as to yield a conversion, preferably a complete conversion,             of the initial products into Li_((4-α))Z_(α)Ti₅O₁₂, and             the source of at least one metal Z being added to the             reaction mixture, preferably in step a) of said process in a             content that is preferably from 0.1 to 2% by weight,             expressed with respect to the mass of said ternary mixture.

Operating conditions that make possible the specific preparation of particles of the formula Li_((4-α))Ti₅O₁₂ are, more specifically, a control of the initial quantities of each of the compounds present in the ternary mixture that is used for preparation of the dispersion.

According to another embodiment, the process of the invention makes possible the synthesis of particles of the formula Li₄Z_(β)Ti_((5-β))O₁₂ (preferably with spinel structure), wherein β is greater than 0 and less than or equal to 0.5, coated with carbon, Z representing a source of at least one metal, preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni, Co, said particles comprising from 0.01 to 10%, preferably 1 to 6%, and still more preferably around 2% by weight of carbon, the quantity of carbon being expressed with respect to the total mass of Li₄Z_(β)Ti_((5-β))O₁₂ particles;

-   -   said process comprising the steps of         -   a) preparation of a dispersion of an intimate ternary             mixture of TiO_(x)—LiY-carbon, wherein             -   x represents a number between 1 and 2,             -   z represents 1 or 2, and             -   Y represents a radical chosen among CO₃, OH, O AND TiO₃                 or a mixture of them; and         -   b) heating of the dispersion obtained in the preceding step,             preferably to a temperature comprised between 400 and 1,000°             C.,             the operating conditions, more specifically the             concentration conditions of components of the ternary             mixture submitted to dispersion, being chosen in such a way             as to yield a conversion, preferably a complete conversion,             of the initial products into Li₄Z_(β)Ti_((5-β))O₂, and the             source of at least one metal Z being added to the reaction             mixture, preferably in step a) of said process in a content             that is preferably from 0.1 to 2% by weight, expressed with             respect to the mass of said ternary mixture,             the operating conditions that make possible the specific             preparation of particles of the formula             Li₄Z_(β)Ti_((5-β))O₁₂ are, more specifically, a control of             the initial quantities of each of the constituents present             in the ternary mixture that is used for preparation of the             dispersion.

According to an advantageous embodiment of the process, the dispersion of the ternary mixture is heated at a temperature of around 600° C.

Still more advantageously, the dispersion is heated in two steps, the first step being carried out until the dispersion reaches a temperature of about 400° C., the second step being carried out at approximately 600° C.

The first step is preferably carried out by rapid heating at around 400° C., preferably during a period of 1 to 4 hours.

The second step is carried out by slow heating, preferably for at least four hours.

According to another advantageous embodiment of the process, at least one step, which is preferably step a), is carried out in air.

According to another advantageous embodiment of the process, at least one step, which is preferably step b), is carried out at least partially in inert atmosphere.

The dispersion of the ternary mixture is advantageously prepared using water and/or at least one solvent that is preferably an organic solvent. This organic solvent is advantageously chosen from the group made up of ketones, saturated hydrocarbons, unsaturated hydrocarbons, alcohols and mixtures of them, still more preferably the dispersion of the ternary mixture is prepared using water, acetone, heptane, toluene or using a mixture of them.

Said dispersion is also prepared dry, without solvent.

According to another preferred embodiment, a compound Li_(z)Y, which comprises at least one compound chosen from the group made up of Li₂O, Li₂CO₃ and LiOH, is chosen. Still more preferably, the Li_(z)Y compound comprises exclusively Li₂CO₃, said Li₂CO₃ preferably being present in a ratio of 25 to 30% by weight with respect to the total mass of the ternary mixture.

Advantageously, the dispersion is carried out by mechanical milling, preferably by high-energy mechanical milling, preferably dry and/or by Jar milling, preferably with a solvent.

According to another preferred embodiment, a TiO_(x) compound of the anatase or rutile TiO₂ type (preferably the anatase TiO₂ type), or a mixture of both, is chosen and TiO₂ is preferably present in said ternary mixture in concentrations of 58 to 71% by weight.

The compound Li_(z)Y preferably comprises Li₂TiO₃, this Li₂TiO₃ preferably being present in a quantity of 43 to 48% by weight of Li₂TiO₃ with respect to the total mass of the ternary mixture.

The carbon used to carry out the process according to the invention may come from any source. Advantageously, the carbon is chosen from the group made up of natural or artificial graphite, carbon black (preferably acetylene black), Shawinigan black, Ketjen black and cokes (preferably petroleum coke) and is added to the reaction mixture, preferably at the beginning of the preparation of the dispersion of the ternary mixture.

The carbon can also be produced in the course of said process, preferably from at least one free organic material, such as a polymer, present in the reaction mixture.

The carbon can also be produced at the surface of the particles by calcination of an organic and/or inorganic material deposited, in the course of said process, on the surface of the Li₄Ti₅O₁₂ particles and/or on the surface of the particles based on Li₄Ti₅O₁₂ and/or on the surface of at least one of the reagents used (preferably the TiO₂) for the preparation of the dispersion of said ternary mixture.

Preferably, the carbon used is in the form of particles having a specific surface area greater than or equal to 2 m²/g, preferably in the form of particles having a specific surface area greater than or equal to 50 m²/g.

According to an advantageous embodiment, the process of the invention is carried out in the presence of an atmosphere containing oxygen, a part of the carbon present in the reaction mixture then being consumed during said process.

According to another advantageous embodiment, the coating of carbon is obtained from the presence, in the reaction mixture, of a powder of Shawinigan carbon and/or at least one polymer, which is preferably a polyol or a polyethylene-polyoxide ethylene copolymer.

According to another advantageous embodiment, as an initial product TiO₂ that is coated with at least one inorganic material, with an inorganic material that preferably comprises an aluminum oxide and/or a zirconium oxide and still more preferably at least one organic material that comprises Al₂O₃ and/or ZrO₂, is used. According to another variation, TiO₂ that is coated with a hybrid inorganic-organic material is used.

A second object of the present invention is made up of particles that can be obtained by use of one of the processes previously defined for the first object of the invention.

These particles comprise a core coated with carbon, the core of said particles being:

-   -   based on Li₄Ti₅O₁₂; or     -   based on Li_((4-α))Z_(α)Ti₅O₁₂, wherein α is greater than zero         and less than or equal to 0.33, Z representing a source of at         least one metal, preferably chosen from the group made up of Mg,         Nb, Al, Zr, Ni, Co; or     -   based on at least one compound of the formula         Li₄Z_(β)Ti_((5-β))O₁₂ with β greater than 0 and/or less than or         equal to 0.5, Z representing a source of at least one metal,         preferably chosen from the group made up of Mg, Nb, Al, Zr, Ni,         Co.

A preferred sub-family is made up of particles wherein the core mainly comprises preferably at least 65% of Li₄Ti₅O₁₂, of Li_((4-α))Z_(α)Ti₅O₁₂ or Li₄Z_(β)Ti_((5-β))O₁₂ or a mixture of these.

The complement notably being made up of TiO₂ Li₂TiO₃ or the residues of solvents.

Still more advantageously, the core of the particles according to the invention is exclusively made up of Li₄Ti₅O₁₂, of Li_((4-α))Z_(α)Ti₅O₁₂ or Li₄Z_(β)Ti_((5-β))O₁₂ or a mixture of these.

A preferred sub-family of particles of the present invention is made up of particles that have a reversible capacity, measured according to the method defined in the description, which is between 155 and 170 mAh/g.

According to an advantageous method, these particles are made up of a core of Li₄Ti₅O₁₂ coated with a layer of carbon.

The particles according to the invention are preferably nanostructures. Their size, measured with scanning electron microscopy, is preferably comprised between 10 and 950 nanometers.

The particles according to the present invention are also characterized by their core, which has a size measured using scanning electron microscopy that is preferably comprised between 10 and 500 nanometers.

The carbon coating that covers these particles is characterized by a thickness that, also measured using scanning electron microscopy, is comprised between 10 and 450 nanometers, still more preferably the thickness of the coating varies between 20 and 300 nanometers.

A third object of the present invention is made up of a cathode of an electrochemical generator (preferably a recyclable type electrochemical generator) comprising particles such as previously defined in the second object of the present invention and/or such that can be obtained by using any one of the processes according to the first object of the present invention.

A fourth object of the present invention is made up of an anode for an electrochemical generator (preferably a recyclable type electrochemical generator) comprising particles such as previously defined in the second object of the present invention and/or such that can be obtained by using any one of the processes according to the first object of the present invention.

A fifth object of the present invention is made up of an electrochemical generator (preferably of the rechargeable type) of the lithium type comprising an anode of the metallic lithium type and a cathode of the Li₄Ti₅O₁₂ type and/or of the Li_((4-α))Z_(α)Ti₅O₁₂ type and/or of the Li₄Z_(β)Ti_((5-β))O₁₂ type or mixtures of them, the cathode in this battery being such as previously defined in the third object of the present invention.

A sixth object of the present invention is made up of an electrochemical generator (preferably of the rechargeable type) of the lithium-ion type comprising an anode of the Li₄Ti₅O₁₂ type and/or the Li_((4-α))Z_(α)Ti₅O₁₂ type and/or the Li₄Z_(β)Ti_((5-β))O₁₂ type or mixtures of them and a cathode of the LiFePO₄, LiCoO₂, LiCoPO₄, LiMn₂O₄ and/or LiNiO₂ type or mixtures of them wherein the anode is such as defined in the third object of the present invention.

Preferably, such a generator uses, in the anode and/or in the cathode, a current collector of solid aluminum or of the Exmet type (expanded metal).

A preferred sub-family of the electrochemical generators according to the present invention is made up of generators that do not require any prior forming of the battery.

A seventh object of the present invention is made up of a hybrid-type supercapacitor comprising an anode of the Li₄Ti₅O₁₂ type and/or the Li_((4-α))Z_(α)Ti₅O₁₂ type and/or the Li₄Z_(β)Ti_((5-β))O₂ type and a cathode of the graphite or carbon type with a large specific surface area, wherein the anode is as defined previously, not requiring any preliminary forming of the supercapacitor.

According to an advantageous embodiment, the anode and/or the cathode of such a supercapacitor is (are) equipped with a current collector of solid aluminum or of the Exmet (expanded metal) type.

According to a preferred embodiment, the electrolyte used in the electrochemical generator or in the supercapacitor is dry polymer, gel, liquid or ceramic in nature.

The Invention is More Specifically Carried Out According to One of the Operating Methods Explained Below: 1—In the Presence of Carbon Powder

The present invention makes available a new synthesis method for Li₄Ti₅O₁₂ that is simple, fast and less costly. The synthesis is based on a ternary mixture of TiO₂ with anatase or rutile structure, of Li₂CO₃ and carbon. The mixture is well dispersed, then submitted to a heating phase that comprises two steps. The first step is rapid heating to 400° C. in air. This temperature stage helps, on one hand, to eliminate the traces of heptane when this solvent is used and, on the other hand, to stimulate the release of CO₂. The second step to 600° C. is longer and requires a minimum of 4 hours. This completes the transformation of the ternary mixture to Li₄Ti₅O₁₂ with spinel structure. The fineness of the particle size is obtained due to a longer heating time during the second step (see the illustration given in FIG. 2).

Carbon plays a crucial role in the synthesis (for this subject, see FIG. 3). In the first place, the carbon is oxidized with the oxygen in the air, with oxygen coming from TiO₂ while releasing CO₂. In the second place, titanium reacts with lithium, forming lithiated titanium. The latter oxidizes with air. The synthesis reaction can be schematically illustrated as follows:

5TiO₂+XC+2Li₂CO₃→Li₄Ti₅O₁₂+(X+2)CO₂  (2)

An excess of carbon is used to ensure complete transformation. In fact, carbon burns in the presence of air, then its excess reduces TiO₂ and Li₂CO₃. In this invention, carbons that contain oxygen groups at the surface are used. The latter react with the lithium oxide. The TiO₂-carbon-Li₂CO₃ mixture can be produced using two methods: in a solvent or in a dry mixture dispersed mechanically. Once the intimate homogeneous powder is obtained, the carbon will play the essential role established according to reaction (2) by obtaining a Li₄Ti₅O₁₂ product without impurities.

The use of Li₂O instead of Li₂CO₃ works well, however with the least trace of humidity there will be formation of LiOH, which reduces the Li₄Ti₅O₁₂ production yield and makes it necessary to maintain the synthesis at 800° C.

The synthesis was also carried out with the TiO₂—Li₂CO₃-carbon mixture dispersed by high-energy mechanical milling (HEMM). The main step before the passage to HEMM is to disperse the ternary mixture well in order to obtain a homogeneous mixture (FIG. 10). For this, first a co-milling for 15 minutes to 2 hours is used, in addition, this co-milling also helps to lower the synthesis temperature. This process produces particles on the nanostructure scale of Li₄Ti₅O₁₂ (FIGS. 6, 7 and 8), compared to the classic method that makes it possible to carry out the formation of the macroscopic particles (FIGS. 4 and 5). The use of these nanostructure particles makes it easier to spread thin electrodes and increases the diffusion of lithium in the spinel structure for power applications. The Li₄Ti₅O₁₂ applications are presented in FIG. 1. In the case where Li₄Ti₅O₁₂ is a cathode, the battery produces 1.5 volts, due to the rechargeability of the Li₄Ti₅O₁₂, this system becomes very interesting for the rechargeable battery markets, thus replacing the large market of primary alkaline batteries of 1.5 volt.

Li₄Ti₅O₁₂ is a white insulating powder, in order to increase its electronic conductivity, it is co-milled with carbon. The latter coats the particles of Li₄Ti₅O₁₂ and gives a good conductivity to the electrode at the time of intercalation and disintercalation of lithium and keeps its capacity (mAh/g) stable at elevated currents (mA/g). In fact, carbon plays a double role in this invention, on one hand, it helps to synthesize a final pure product of the Li₄Ti₅O₁₂ type by lowering the synthesis temperature, and on the other, it increases the electronic conductivity by co-milling with Li₄Ti₅O₁₂ for manufacturing electrodes for an electrochemical generator.

2—In the Presence of Organic Coating on the Surface of the TiO₂ Particles

The synthesis of the TiO₂ mixture coated with organic material (produced by the Kronos company) with Li₂CO₃. The two components are diluted in water. The intimate mixture is obtained by Jar milling for 24 hours. The paste obtained is dried at 120° C. during 12 hours. The mixture is dispersed by “vapour jet milling from the Kronos company.” A two stage thermal treatment, 400 and 850° C. in inert atmosphere, yields particles of nano-Li₄Ti₅O₁₂ coated with carbon (FIG. 16).

3. In the Presence of Free Organic Material in the Mixture

The synthesis of the mixture of standard TiO₂ and an organic material (polyol, PE-PO or other) with Li₂CO₃ or LiOH (or mixtures of them. The three components are diluted in water. The intimate mixture is obtained by Jar milling over 24 hours. The paste obtained is dried at 120° C. during 12 hours. The mixture is dispersed by “vapour jet milling from the Kronos company.” A two stage thermal treatment, 400 and 850° C. in inert atmosphere, yields nano-particles of Li₄Ti₅O₁₂ coated with carbon.

4. In the Presence of Inorganic Coating on the Surface of TiO₂ Particles

The synthesis of the mixture of TiO₂ coated with an inorganic material of the type Al₂O₃, ZrO₂ and the like (product from the Kronos company) with Li₂CO₃ or LiOH (or a mixture of them). The two components, mixed with the organic material are diluted in water. The intimate mixture is obtained by Jar milling during 24 hours. The paste obtained is dried at 120° C. during 12 hours. The mixture is dispersed by “vapour jet milling from the Kronos company.” A two stage thermal treatment, 400 and 850° C. in inert atmosphere, yields particles of Li_((4-α))Z_(α)Ti₅O₁₂ or of Li₄Z_(β)Ti_((5-β))O₁₂ coated with carbon (FIG. 17).

5. In the Presence of Hybrid Organic-Inorganic Coating on the Surface of TiO₂ Particles

The synthesis of the mixture of TiO₂ coated with hybrid organic-inorganic material of the polyol type, preferably a high purity polyol, still more preferably trimethylpropane or an ethylene polyethylene-polyoxide copolymer, Al₂O₃, ZrO₂ or the like (product from the Kronos company) with Li₂CO₃ or LiOH (or a mixture of them). The two components are diluted in water. The intimate mixture is obtained by Jar milling for 24 hours. The paste obtained is dried at 120° C. for 12 hours. The mixture is dispersed by vapour jet milling from the Kronos company. Thermal treatment at two stages, of 400 and 850° C. in inert atmosphere, yields nano-particles of Li_((4-α))Z_(α)Ti₅O₁₂ or of Li₄Z_(β)Ti_((5-β))O₁₂ coated with carbon (FIG. 18).

6. Use of Nano-Li₄Ti₅O₁₂ Coated with Carbon as an Anode in Hybrid Supercapacitor Technology (HSC)

This technology (FIG. 12) uses an insertion anode of the Li₄Ti₅O₁₂ type placed face to face with a cathode of the graphite or carbon type with large specific surface area (double layer) with a polymer, gel, liquid or ceramic electrolyte. The advantage of nano-Li₄Ti₅O₁₂ coated with carbon (FIG. 11) promotes the diffusion of lithium inside the spinel structure, and in particular, at elevated currents like 12 C (charge-discharge in 5 minutes). At these ratings, the HSC develops 90% of the nominal capacity. The presence of carbon provides good conductivity at the grain level and on the scale of the electrode, which limits the addition of large proportions of carbon to the electrode. This makes it possible to increase the energy density of the HSC.

HSC technology uses two collectors of the Exmet (expanded metal) type in aluminum with an electrolyte having a salt mixture of LiTFSI+LiBF₄ or LiTFSI+LiPF₆ or LiTFSI+BETi+LiBF₄. This mixture makes it possible to have good ionic conductivity and reduces the collector corrosion during high-voltage charging. The energy density of the HSC is around 60 Wh/kg and the capacity obtained is 90% at charging rates of 12 C. HSC technology presents an energy density comparable to Pb-acid or Ni—Cd technologies, in addition this technology has a long cyclability.

It is important to keep in mind that Li-ion technology (graphite/LiCoO₂) is limited to currents less than 2 C (30 minutes) and by the number of cycles which is 1200.

EXAMPLES

The following examples are given purely as an illustration and should not be interpreted as constituting any limitation whatsoever of the invention.

Example 1 Preparation in the Presence of Heptane of Particles of Li₄T₅O₁₂ Coated with Carbon

23 g of TiO₂ with anatase structure (commercialized by the Kronoss Company, Varennes, Canada under the name XP-406) are mixed with 10 grams of Li₂CO₃ (Aldrich, Canada) and with 20 grams of Shawinigan black. An excess of carbon black is used to ensure complete transformation of the CO₂ and lower the synthesis temperature.

This ternary mixture is placed in a steel container and heptane is added in a powder/liquid ratio of around 35 g/150 ml. The heptane is used to reduce the heat and the friction between the particles of powder and the balls and leaves the product inert. Stainless steel balls are added to homogenize the ternary mixture. After 2 hours of intimate co-milling, a powder with fine particle size is obtained. The success of the co-milling depends on lowering the synthesis temperature. The heating of this co-milled mixture is carried out in two steps. The first step is a rapid heating to 400° C. in air. This temperature stage promotes the elimination of traces of heptane and stimulates the start of CO₂ release. It was proven by the loss of weight shown by TGA (Perkin thermal analysis), which is shown in FIG. 13. The second stage consists of slow heating to 600° C. This completes the transformation of the product into Li₄Ti₅O₁₂ with spinel structure. The X-ray spectrum reveals the presence of peaks characteristic of the Li₄Ti₅O₁₂ structure.

Example 2 Dry Preparation of Particles of Li₄Ti₅O₁₂ Coated with Carbon

23 g of TiO₂ with anatase structure (XP-406 from the Kronos Company, Varennes) are mixed with 10 grams of Li₂CO₃ (Aldrich, Canada) and with 20 g of Shawinigan black. Again an excess of carbon black is used to ensure complete transformation of the CO₂ and lower the synthesis temperature. This ternary mixture is placed in a dry container with stainless steel balls.

After 2 hours of intimate milling, a powder with a fine particle size is obtained. Heating of this co-milled mixture is carried out in two steps, at 400° C. and then at 600° C. The X-ray spectrum reveals the presence of a spinel structure for the Li₄Ti₅O₁₂ particles thus synthesized.

Example 3 Dry Preparation and Characterization of Nano-Particles of Li₄T₅O₁₂ Coated with Carbon

23 g of TiO₂ with anatase structure (XP-406 from the Kronos Company, Varennes) are mixed with 10 grams of Li₂CO₃ (Aldrich, Canada) and with 2 grams of Shawinigan black. A 6-gram excess of carbon black is again used to ensure complete transformation of the CO₂ and to lower the synthesis temperature. This ternary mixture is subject to high-energy mechanical milling (using a shaker mill machine of the type SPEX 8000) in the presence of stainless steel balls in a ball:powder ratio of 10:1. The milling period can vary between 3 minutes and 3 hours, which in the case of the present example is 2 hours. Heating of the co-milled mixture is carried out in two steps. The first step consists of rapid heating to 400° C. in air. The second step consists of slow heating to 600° C. This completes the transformation of the product into Li₄Ti₅O₁₂ with spinel structure. The X-ray spectrum confirms the presence of peak characteristics of the spinel structure of the Li₄Ti₅O₁₂.

FIG. 15, which is a photograph obtained using scanning electron microscopy, shows that the particles of Li₄Ti₅O₁₂ are of nanoscopic size. FIG. 14 relates to a photo obtained in the same manner, but for particles prepared without the addition of carbon shows that the corresponding particles are of macroscopic size.

Example 4 Preparation and Evaluation of an Electrode Containing Particles of Li₄Ti₅O₁₂ Coated with Carbon

According to the synthesis process used in example 1, the particles of Li₄Ti₅O₁₂, of poly(vinylidene fluoride) (PVDF) and Ketjen black, present in a mass ratio of 87/10/3 are mixed. This mixture is applied to an exmet electrode of aluminum, then heated for 12 hours with nitrogen scavenging. The electrode thus prepared is then heated for 2 hours in vacuum.

The electrode is then assembled in an electrochemical cell of around 4 cm² with a Celgard type separator facing the lithium metal. The solvent is of the TESA type (tetra ethyl sulfone amine) ethylene carbonate type with LiTFSI salt (lithium trifluoromethanesulfonimide). The cycling is carried out, at ambient temperature, between 1.2 and 2.5 V. The reversible capacity obtained is 155 mAh/g with an average voltage of 1.55 V.

Example 5 Providing Evidence of the Importance of Good Homogenization of the Ternary Mixture

According to the synthesis process described in example 1 above, Li₄Ti₅O₁₂ and Ketjen black, in a volume ratio 40/3, are co-milled in heptane in the presence of stainless steel balls. The mixture is dried, then mixed with a polymer solution based on a polyether marketed by the Baker Hughes Company, USA under the commercial name UNITHOX 750, in a volume ratio 43/57. This mixture is then applied to an aluminum collector, then heated for 12 hours with nitrogen scavenging. The collector thus processed is then heated for 2 hours in vacuum.

The electrode is assembled in an electrochemical cell with about 4 cm² surface area with a separator of the polymer type based on salt containing polyether prepared in a laboratory, with LiTFSI salt (tetra fluoro sulfur lithium imide) placed face to face with the lithium metal as anode. Cycling is carried out at 80° C. between 1.2 and 2.5 V. The reversible capacity obtained is 155 mAh/g in C/24 and it is 96% of the nominal capacity obtained with a rapid rating in C/1. The cell thus prepared demonstrates good cycling stability, more than 1500 cycles in C/1.

The use of co-milling and carrying out of a good intimate dispersion between the Li₄Ti₅O₁₂ oxide and the carbon black ensures the reproducibility of the results.

On the other hand, if the Li₄Ti₅O₁₂ oxide is mixed without co-milling with the carbon black and the polymer, in a volume ratio 40/3/57 and if this mixture is applied to an aluminum collector, then heated for 12 hours with nitrogen scavenging and then heated for 2 hours in a vacuum, the electrochemical result obtained by introduction of this electrode in a cell without solvent (completely solid) comprising a polymer (polyether) at 80° C. is 150 mAh/g in C/24 while only 75% of the nominal value is found with fast loading in C/1. In fact, this is due to the poor dispersion between the oxide and the carbon black. In addition, the reproducibility of the results is uncertain.

Example 6 Preparation of Li₄Ti₅O₁₂ Using a Binary Mixture of LiOH—TiO₂

In this example, particles of Li₄Ti₅O₁₂ were prepared using a binary mixture of LiOH—TiO₂ (anatase) of 10.5 and 16 g, respectively, heated for 18 hours in air. The X-ray spectrum obtained for these particles establishes the presence of peak characteristics of the spinel structure of Li₄Ti₅O₁₂ as well as the presence of traces of TiO₂ (rutile) and Li₂TiO₃.

The Li₄Ti₅O₁₂ powder obtained is mixed with PVDF and with Shawinigan black in a weight ratio 87/10/3. This mixture, which makes up the electrode, is applied to an aluminium Exmet support, then heated for 12 hours with nitrogen scavenging. The electrode thus obtained is then heated for 2 hours in vacuum. Said electrode is assembled in an electrochemical cell about 4 cm² with a Celgard type separator placed face to face with lithium metal as anode. The solvent used is of the TESA type (tetra ethylsulfamide)-ethylene carbonate (1:1 by volume) with 1 mol of LiTFSI (bis(trifluoromethane sulfonimide)).

The reversible capacity obtained in this case is 140 mAh/g. The capacity obtained by the binary type synthesis is thus appreciably less than that obtained by the using ternary synthesis in the presence of carbon.

Example 7 Preparation of Li₄Ti₅O₁₂ Particles Coated with Carbon with PVDF and Shawinigan Black

According to the synthesis of example 1, Li₄Ti₅O₁₂ particles are mixed with PVDF and Shawinigan black in a weight ratio 87/10/3. This mixture is applied on an aluminium Exmet type electrode, then heated for 12 hours with nitrogen scanning. All of this is then heated for 2 hours in vacuum.

Cobalt oxide LiCoO₂ is mixed with PVDF and Shawinigan black in a weight ratio 87/10/3. Then the mixture thus obtained is applied to an aluminum Exmet type electrode, the assembly thus obtained is then heated for 12 hours with nitrogen scanning, then in a second step is heated for 2 hours in vacuum.

The Li₄Ti₅O₁₂ electrode is assembled in a lithium-ion battery face to face with the LiCoO₂ electrode as cathode with a Celgard type separator. The solvent used is of the ethylene carbonate-methyl ethylene carbonate type (1:1 by volume) with 1 mole of lithium bis(trifluoromethane sulfonimide).

The battery voltage tends toward zero volts (33 mV). The battery is cycled between 1.2 V and 2.8 V. The average voltage is around 2.5 V. The irreversible capacity of the first cycle is around 2%. This irreversibility is minimum compared to the conventional carbon/LiCoO₂ system. Because of the fact that the two electrodes of the Li₄Ti₅O₁₂/LiCoO₂ system have no passivation film, the reversible capacity of the battery is stable for more than 500 cycles. Knowing that 2.5 V yields 70% of the average voltage of the lithium-ion system of the carbon/LiCoO₂ type, a 30% deficit remains to be recaptured. The lack of energy to be obtained from the carbon/LiCoO₂ system can be filled by:

-   -   an Exmet type collector based on aluminum on the anode that         makes it possible to reduce the weight of the battery         (conventional carbon/LiCoO₂ system using copper as current         collector for the anode);     -   decrease in the quantity of LiCoO₂ (absence of irreversibility)         while in the classic system, the carbon type anode consumes an         irreversible capacity of around 20% to form the passivation         film;     -   increase in the energy of the Li₄Ti₅O₁₂ system by using olivine         phosphate of the LiCoPO₄ type at high voltage or lithium         manganese with high voltage in the cathode;     -   use of a thin separator of 10 to 15 microns; and     -   simplified thin packaging of the plastic metal type.

Example 8 Preparation of an Electrochemical Cell Using a TESA Type Solvent

According to the operating method used in example 1, Li₄Ti₅O₁₂ is mixed with PVDF and Shawinigan black in a weight 87/10/3. This mixture is applied to an aluminium Exmet type electrode.

The assembly thus obtained is heated for 12 hours with nitrogen scavenging, then for 2 hours.

Natural graphite NG7 (Kansai Coke, Japan) is mixed with PVDF in a weight ratio 90/10. This mixture is applied to an aluminium Exmet type electrode. The assembly thus obtained is heated for 12 hours with nitrogen scavenging, then heated 2 hours in vacuum.

The Li₄Ti₅O₁₂ electrode is mounted face to face with the graphite electrode separated by a Celgard. The solvent used is PC+EC+TESA (1:1:1 by volume) containing 1 mol of LiPF₅+LiTFSI.

In this example, the graphite electrode is used as cathode and the intercalation reaction is an electrolytic reaction of the double layer, of which the anion PF₆ is absorbed at the surface of the graphite. The voltage cycling limits are between 1.5 V and 3.0 V, for an average voltage of 2.25 V. This average voltage value increases the energy density by 50% with respect to values obtained with a conventional carbon-carbon system.

The efficiency of the first cycle is 96%. After 200 cycles, no loss of capacity was observed.

Example 9 Preparation of Li₄Ti₅O₁₂ Particles Coated with Carbon Using a Polyol as a Carbon Source

87 g of particles of TiO₂ with anatase structure coated with polyol (type XP-413 from the Kronos Company in Varennes) are mixed with 35.4 g of Li₂CO₃ (Limetech, Canada). The mixture of these two compounds is carried out in the presence of water using Jar milling. The mixture-zircon balls-free volume ratio is 1/3-1/3-1/3. Milling time is 24 h. The paste obtained is dried at 120° C. for 12 hours. Calcination of the powder obtained is carried out in a rotary kiln (fabricated in-house) in two temperature stages. The first stage is at 400° C. for one hour and the second stage at 850° C. for 3 hours in a controlled nitrogen atmosphere. The analysis by X-ray diffraction of the powder synthesized clearly shows that nano-particles of Li₄Ti₅O₁₂ with spinel structure are obtained (as established using SEM). The analysis of carbon content carried out by the carbon sulfur detector method (model CS444, Leco, USA) clearly shows that a quantity of 2% by weight remains in the Li₄Ti₅O₁₂ structure.

Example 10 Preparation of Li₄Ti₅O₁₂ Particles Using Polyethylene Glycol as a Source of Carbon

87 grams of TiO₂ with anatase structure (XP-406 from the Kronos Company, Varennes) are mixed with 35.4 g of Li₂CO₃ (Limetech, Canada) and with 8 grams of PE-PO. The three compounds are mixed in the presence of water using Jar milling. The mixture-zircon balls-free volume ratios are 1/3-1/3-1/3. The milling time is 24 hours. The paste obtained is dried at 120° C. for 12 hours. Calcination of the powder obtained is carried out in a rotary kiln (fabricated in-house) in two temperature stages. The first is at 400° C. for one hour and the second at 850° C. for 3 hours in a controlled nitrogen atmosphere. Analysis by X-ray diffraction of the synthesized powder clearly shows that a spinel structure with nano-particles of Li₄Ti₅O₁₂ is obtained, the size of the particles is established using SEM. Analysis of carbon content obtained is carried out using the carbon sulfur detector method (model CS444, Leco, USA). It clearly shows that 2% by weight of carbon remains present in the Li₄Ti₅O₁₂ structure.

Example 11 Preparation of Particles of Li₄Ti₅O₁₂ Coated with Carbon by Calcination and Using Coated TiO₂ Particles

87 grams of TiO₂ particles with anatase structure coated with Al₂O₃ (type XP-414 from the Kronos Company, Varennes) are mixed with 35.4 grams of Li₂CO₃ (Limetech, Canada) and with 7 grams of Shawinigan black. The three compounds are mixed in the presence of water using Jar milling. The mixture-zircon balls-free volume ratios are 1/3-1/3-1/3. The milling time is 24 hours. The paste obtained is dried at 120° C. for 12 hours. Calcination of the powder obtained is carried out in a rotary oven (fabricated in-house) in two temperature stages. The first stage is at 400° C. for one hour and the second stage is at 850° C. for 3 hours in a controlled nitrogen atmosphere. Analysis by X-ray diffraction of the synthesized powder clearly shows that a spinel structure with nano-particles of Li₄Ti₅O₁₂ is obtained, the size of the particles is measured using SEM. Analysis of the carbon content obtained is carried out using the carbon sulfur detector method (model CS444, Leco, USA). It clearly shows that 1.95% by weight of carbon remains present in the Li₄Ti₅O₁₂ structure.

Example 12 Preparation of Li₄Ti₅O₁₂ Particles from Particles of TiO₂ Coated with an Al₂O₃-Polyls Mixture

87 grams of TiO₂ with anatase structure coated with an Al₂O₃-polyols mixture (of XP-415 type from the Kronos Company, Varennes) are mixed with 35.4 g of Li₂CO₃ (Limetech, Canada) and with 7 grams of Shawinigan black. The three compounds are mixed in the presence of water using Jar milling. The mixture-zircon balls-free volume ratios are 1/3-1/3-1/3. The milling time is 24 hours. The paste obtained is dried at 120° C. for 12 hours. Calcination of the powder obtained is carried out in a rotary oven (fabricated in-house) in two temperature stages. The first is at 400° C. for one hour and the second at 850° C. for 3 hours in a controlled nitrogen atmosphere. Analysis by X-ray diffraction of the synthesized powder clearly shows that a spinel structure with nano-particles of Li₄Ti₅O₁₂ is obtained; the size of the particles is measured using SEM. Analysis of the carbon content obtained is carried out using the carbon sulfur detector method (model CS444, Leco, USA). It clearly shows that 1.95% by weight of carbon remains present in the Li₄Ti₅O₁₂ powder.

Example 13 Preparation of a Battery with Li₄Ti₅O₁₂ Particles Coated with Carbon and with EC+PC+DMC as Solvent

According to the operating method of example 1, Li₄Ti₅O₁₂ is mixed with PVDF and Shawinigan black in a weight ratio 87/10/3. This mixture is applied to an aluminium Exmet electrode. All of this is heated for 12 hours with nitrogen scavenging, then for 2 hours in vacuum.

Carbon with a large specific surface area (PICA, FRANCE) is mixed with PVDF in a weight ratio of 20/80. This mixture is applied to an aluminium Exmet type electrode. All of this is heated for 12 hours with nitrogen scavenging then heated for 2 hours in vacuum.

The Li₄Ti₅O₁₂ electrode is mounted face to face with a carbon electrode as cathode, separated by a Celgard. The solvent used is EC+PC+DMC (1:1:1 by volume) containing 1 mole of LiTFSI+LiBF₄.

In this example, the carbon electrode is used as cathode. The intercalation reaction in this case is a double layer electrolytic reaction, wherein the PF6 and TFSI anions are absorbed at the carbon surface. The cycling voltage limits are between 1.5 V and 3.0 V with an average potential of 2.25 V. This average voltage value increases the energy density by 50% comparatively to the conventional carbon-carbon system.

The efficiency of the first cycle is 96%. After 200 cycles, no capacity loss has been observed.

Example 14 Preparation of a Battery from Particles of Li₄Ti₅O₁₂ Coated with Carbon

According to the operating method of example 1, Li₄Ti₅O₁₂ is mixed with PVDF and Shawinigan black in a weight ratio 87/10/3. This mixture is applied to an aluminium Exmet electrode. All of this is heated for 12 hours with nitrogen scavenging at a temperature of 120° C., then for 2 hours in vacuum at a temperature of 120° C.

A conductive polymer of the polyaniline type is mixed with PVDF and Shawinigan black in a weight ratio 87:10:3. The mixture thus obtained is applied to an aluminium Exmet electrode, then heated for 12 hours with nitrogen scavenging at a temperature of 120° C., then for 2 hours in vacuum at a temperature of 120° C.

The Li₄Ti₅O₁₂ electrode is mounted face to face with the carbon electrode as cathode separated by a Celgard. The solvent used is EC+PC+DMC (1:1:1 by volume), commonly called, containing 1 mole of LiTFSI+LiBF₄.

In this example, the polymer electrode conductor is used as cathode. The intercalation reaction is then a doping reaction of the PF₆ and TFSI anions across the conductive polymer chains. The cycling voltage limits are comprised between 1.5 V and 3.0 V with an average voltage of 2.25 V. The performance observed is comparable to that obtained in the preceding example.

In conclusion, the particles according to the present invention present a surprisingly notable spreading capacity, an excellent nominal capacity, an excellent cycling stability and a remarkable high current power in electrochemical devices that use them, in particular at the electrode level, as well as flexibility regarding electrode thickness that can be produced using these particles.

Thus at 12 C (5 minutes), the particles in nano form yield 90% of the nominal capacity, while the corresponding macroparticles develop no more than 50% of the capacity. The macros also have a limitation with currents less then 5 C. The nano-particles do not have any limitation.

In addition, if the pretreatment of the initial mixture is not optimized, e.g. if the milling time is less than 15 minutes, the synthesis of the mixture in the presence of carbon gives rise to macroscopic particles.

In addition, diffusion of lithium is faster in the case of nano-particles.

Even though the present invention has been described using specific embodiments, it is understood that many variations and modifications could be made to said embodiments, and the present invention covers all such modifications, usages or adaptations of the present invention that generally follow the principles of the invention and including any variation of the present description which become known or are conventional in the field of activity wherein the present invention is used, and which can apply to the essential elements mentioned above, in agreement with the scope of the following claims. 

1. A process for synthesizing, in the presence of oxygen, particles of an oxide corresponding to a formula selected from: Li₄Ti₅O₁₂; Li_((4-α))Z_(α)Ti₅O₁₂, wherein α represents a number greater than zero and less than or equal to 0.33, and Z represents at least one metal; and Li₄Z_(β)Ti_((5-β))O₁₂, wherein β represents a number greater than zero and less than or equal to 0.5, and Z represents at least one metal, said process comprising the steps of: a) preparing an intimately dispersed ternary mixture of TiO_(x)—Li_(z)Y-carbon, wherein x is a number between 1 and 2, z is 1 or 2, Y is a radical chosen from the group consisting of CO₃, OH, O and TiO₃ or a mixture thereof, and the carbon is a carbon powder selected from the group consisting of natural or artificial graphite, carbon black, Shawinigan black, Ketjen black and cokes; b) heating the dispersion at a temperature of between 400 and 1,000° C.; and c) if appropriate, adding a source of at least one metal Z to the ternary mixture, wherein the operating conditions are chosen in such a way as to yield a conversion of the initial products respectively into Li₄Ti₅O₁₂, Li_((4-α))Z_(α)Ti₅O₁₂, Li₄Z_(β)Ti_((5-β))O₁₂.
 2. The process of claim 1, wherein the dispersed ternary mixture is heated at a temperature of about 600° C.
 3. The process of claim 2, wherein the dispersed ternary mixture is heated in two steps, the first step being carried out until the dispersed ternary mixture reaches a temperature of about 400° C. and the second step being carried out until the dispersed ternary mixture reaches a temperature of about 600° C.
 4. The process of claim 3, wherein the first step is carried out by rapid heating to around 400° C.
 5. The process of claim 3, wherein the second step is carried out by slow heating.
 6. The process of claim 3, wherein at least one step of step a) or step b) is carried out in air.
 7. The process of claim 3, wherein at least one step of step a) or step b) is carried out at least in part in inert atmosphere.
 8. The process of claim 1, wherein the dispersed ternary mixture is prepared using water and/or at least one solvent.
 9. The process of claim 1, wherein the dispersed ternary mixture is prepared without solvent.
 10. The process of claim 1, wherein the Li_(z)Y compound comprises at least one compound selected from the group consisting of Li₂O, Li₂CO₃, and LiOH.
 11. The process of claim 10, wherein the Li_(z)Y compound consists of Li₂CO₃.
 12. The process of claim 1, wherein the dispersed ternary mixture is prepared by high energy mechanical milling.
 13. The process of claim 1, wherein TiO_(x) is of the anatase or rutile TiO₂ type, or a mixture of both.
 14. The process of claim 1, wherein the compound Li_(z)Y comprises Li₂TiO₃.
 15. The process of claim 1, wherein the carbon is in the form of particles having a specific surface area greater than or equal to 2 m²/g.
 16. The process of claim 13, wherein the TiO₂ used as an initial product is coated with at least one inorganic material.
 17. The process of claim 13, wherein the TiO₂ used is coated with a hybrid inorganic-organic material.
 18. The process of claim 1, wherein the size of particles in the ternary mixture is between 100 nanometers and 10 micrometers.
 19. The process of claim 1, wherein the concentration of components of the ternary mixture are chosen in such a way as to yield a conversion of the initial products into Li₄Ti₅O₁₂, Li_((4-α))Z_(α)Ti₅O₁₂ or Li₄Z_(β)Ti_((5-β))O₁₂.
 20. Particles of an oxide corresponding to a formula selected from: Li₄Ti₅O₁₂; and/or Li_((4-α))Z_(α)Ti₅O₁₂, wherein π is greater than zero and less than or equal to 0.33 and wherein Z is a source of at least one metal; and/or Li₄Z_(β)Ti_((5-β))O₁₂, wherein β is greater than 0 and/or less than or equal to 0.5 and Z is a source of at least one metal, wherein said particles are obtained by the method of claim
 1. 21. The particles of claim 20, wherein said particles have a reversible capacity between 155 and 170 mAh/g.
 22. The particles of claim 20, wherein said particle has a size between 10 and 950 nanometers.
 23. Particles obtained by the process of claim 1, wherein said particles are nano-particles.
 24. A cathode of an electrochemical generator comprising particles of claim
 20. 25. An anode for an electrochemical generator comprising particles of claim
 20. 26. An electrochemical generator of the lithium type comprising an anode of the metallic lithium type and a cathode of claim 24, wherein said cathode is of the Li₄Ti₅O₁₂ type and/or of the Li_((4-α))Z_(α)Ti₅O₁₂ type and/or of the Li₄Z_(β)Ti_((5-β))O₁₂ type.
 27. An electrochemical generator of the lithium-ion type comprising an anode of claim 25, wherein said anode is of the Li₄T₅O₁₂ type and/or the Li_((4-α))Z_(α)Ti₅O₁₂ type and/or the Li₄Z_(β)Ti_((5-α))O₁₂, and a cathode of the LiFePO₄, LiCoO₂, LiMn₂O₄ and/or LiNiO₂ type.
 28. The electrochemical generator of claim 26, wherein the anode and/or the cathode are equipped with a current collector of solid aluminum or of expanded metal (Exmet) type.
 29. A hybrid-type supercapacitor comprising an anode of claim 25, wherein said anode is of the Li₄Ti₅O₁₂ type and/or the Li_((4-α))Z_(α)Ti₅O₁₂ type and/or the Li₄Z_(β)Ti_((5-β))O₁₂ and a cathode of the graphite or carbon type with a specific surface area, and wherein the supercapacitor does not require any preliminary formation. 